CN109852991A - A kind of CO2Electrochemical reduction electrode and preparation and application - Google Patents
A kind of CO2Electrochemical reduction electrode and preparation and application Download PDFInfo
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- CN109852991A CN109852991A CN201711237054.XA CN201711237054A CN109852991A CN 109852991 A CN109852991 A CN 109852991A CN 201711237054 A CN201711237054 A CN 201711237054A CN 109852991 A CN109852991 A CN 109852991A
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Abstract
The present invention relates to a kind of Carbon dioxide electrochemical reduction electrodes and preparation and application, the decorative layer that electrode is deposited with metal catalytic particles by substrate and thereon to form, and the metal catalytic particles are tapered in nanometer；This feature electrode is obtained using the technology that chemistry displacement reaction is combined with electrochemistry potentiostatic electrodeposition.This tapered catalyst particle structure can increase considerably CO2The reaction rate of electrochemical reduction changes the product distribution of ERC reaction.In addition, the preparation method of this feature electrode provided by the invention is simple, favorable reproducibility, strong operability, it is easy to amplify.
Description
Technical field
The invention belongs to Carbon dioxide electrochemical reduction technical fields, the in particular to electrode in the field.
Background technique
Electrochemical reduction CO2(ERC) technology is to utilize electric energy by CO2Organic chemicals are reduced to, realize CO2It converts and has
Imitate a kind of technology utilized.With other CO2Transformation technology is compared, the outstanding advantage of ERC technology be it is easy to operate, it is at low cost
Honest and clean, using water as protonation hydrogen source, can be realized CO at normal temperatures and pressures2Efficient Conversion, therefore do not need chemistry
Energy consumption caused by hydrogen manufacturing needed for transformation technology and heating, pressurization, equipment investment are few.
Currently, during the research and development of ERC electrode, relate generally to metal electrode, metal-modified electrode and
Three kinds of gas-diffusion electrode.Most study is metal electrode derived from metal oxide in metal-modified electrode therein.This
One outstanding feature of class electrode is that the surface roughness of electrode is very big, and the electrochemical area for participating in reaction dramatically increases, thus
The overpotential for significantly reducing ERC, improves the rate of ERC reaction, while also changing the distribution of reaction products of ERC.Such as
Kanan et al. obtains Au using heat-treating methodsxO and thick Cu2O nano wire, the then in-situ reducing under ERC reaction condition
For Au nanoparticle and Cu nano wire, (J.Am.Chem.Soc.2012,134,19969-19972；J.
Am.Chem.Soc.2012,134,7231-7234), electrochemical surface area improves nearly 480 times, and the overpotential of ERC reaction is significantly
It reduces, target product is based on CO.Woo et al. prepares the Cu of dense arrangement on smooth Cu foil surface using the method for electro-deposition
Column (Jaehoon Chung, Da Hye Won, JaekangKoh, Eun-HeeKimcandSeongIhl Woo,
Phys.Chem.Chem.Phys., the generation overpotential of formic acid 2016,18,6252-6258), is reduced into 250mV, in-0.5V
(vs.RHE) current efficiency of HCOOH reaches 29% under electrolytic potential.The side that the heat treatments such as Wang are combined with electrochemical reduction
Method prepares highdensity Cu nano line electrode (Nano Lett.2015,15,6829-6835), faraday of the electrode to CO
Efficiency reaches 60%, and overpotential only 0.3V, can be obtained 10mAcm-2Kinetic current, show high activity.
Summary of the invention
A kind of CO2Electrochemical reduction electrode, the decorative layer for being deposited with metal catalytic particles by substrate and thereon form,
The metal catalytic particles are tapered in nanometer；Wherein nanometer cone height is 1~10 μm, and cone bottom diameter is 0.2~2 μm, preferably
Bore it is 2~7 μm high, preferably cone bottom diameter be 0.3~1.2 μm.
Loading of the tapered catalyst particle of the nanometer in substrate is 0.1~3.0mg cm-2, preferably loading is
0.5~1.8mg cm-2。
Electrode preparation is combined using chemistry displacement reaction with electrochemistry potentiostatic electrodeposition heating under stirring condition
Technology obtain.Wherein, deposition liquid component includes soluble salt solutions (main salt), template, the complexing agent, stabilization of deposited metal
Agent, reducing agent and additive, main salt: template: the molar ratio control range of additive is 104:103: 1~103:102:
1, preferred proportion range is 0.6 × 104:0.4×103: 1~0.15 × 104: 0.2 × 103:1.Deposit liquid pH range be 8~
10。
The chemistry displacement reaction occurs between the metal of metallic and main salt that template deposits.
The soluble salt solutions of the deposited metal are one of halide, sulfate, nitrate, acetate；It is heavy
The concentration of metal ions is 0.5mM~50mM in hydrops, and preferred ion concentration is 5mM~30mM；
The template is one of nickel nitrate, nickel chloride, nickel sulfate；
The reducing agent is soluble hypophosphite, including sodium hypophosphite, ammonium hypophosphite, ortho phosphorous acid potassium
One of, wherein Hypophosphite concentration is 0.05M~1.0M in deposition liquid, and preferred concentration range is 0.1M~0.5M；
The stabilizer is boric acid, and depositing concentration in liquid is 0.05M~5M, and preferred concentration is 0.1M~2M；
The complexing agent is citric acid or citrate, including one in ammonium citrate, sodium citrate, potassium citrate
Kind；The concentration for depositing citrate in liquid is 5mM~100mM, and preferred concentration is 10mM~50mM；
The additive is polyethylene glycol type surfactant, including molecular weight is lower than 20,000 polyethylene glycol
(PEG), oleyl alcohol, Qula lead to one of Triton-100.
The electro-deposition current potential lower than the equilibrium potential of corresponding deposited metal about 0.3~1.0V, sedimentation time are
5min~90min, preferred deposition time are 10min~60min.
The electrode preparation includes the following steps:
1) processing of impurity is removed to substrate；It is dried up after being rinsed with water after processing to neutrality with inert atmosphere；
The base material is metal or charcoal based porous materials, and the metal is one of Cu, In, Ag, Au or two
Kind or more, metal quality content is not less than 99.5%；Charcoal based porous materials are one of carbon paper, carbon felt or carbon cloth, porosity
60%~95%；Shapes of substrates is flake, thickness 0.05mm-2mm；
The base material decontamination processing, including oil removing and chemical treatment；Wherein, oil removal process is at room temperature in pole
At least 30min is impregnated in property solvent；Chemical treatment is impregnates in the hydrochloric acid solution that mass concentration is 1%~38%, when immersion
Between be 5min~60min, dried up after being cleaned up after processing with inert atmosphere.
The polar solvent is one of dehydrated alcohol, acetone, and inert atmosphere is one of nitrogen, argon gas or two
Kind or more.
2) base material is immersed in deposition liquid, adjusting bath temperature and mixing speed, carries out chemistry displacement and perseverance
Potential deposition is dried up after being rinsed with water to neutrality after deposition with inert atmosphere；Surface is obtained with the tapered catalyst of compact nanometer
The electrode of particle；
The plating solution pH value adjustment uses concentrated ammonia liquor or the hydroxide of alkali metal.
The electrodeposition temperature is 40 DEG C~80 DEG C, and mixing speed is 200rpm~800rpm.
3) there is the electrode of the tapered catalyst particle of compact nanometer to carry out electrochemical reduction pretreatment surface, obtains CO2
Electrochemical reduction electrode.
The electrochemical reduction is pre-processed in CO2It is carried out in the salting liquid of saturation, the salting liquid is that concentration is
The sodium bicarbonate or saleratus of 0.1~0.5M；The electrochemical reduction pretreatment, processing electric current are 0.1~0.5mA cm-2, pretreatment time is 20min~60min.
The application of electrode is in Carbon dioxide electrochemical reduction.
Advantages of the present invention and the utility model has the advantages that
The invention discloses the electrode and preparation method thereof that a kind of catalyst particle is in the tapered dense arrangement of nanometer, the electrodes
The characteristics of be the feature high using tapered electrode tip electric field strength, cation concn is big, increase eletrode tip CO nearby2It is dense
Degree, reaches the reaction rate for significantly improving ERC, changes simultaneously the dual purpose of distribution of reaction products.During the preparation process, due to
Metal in template is located at before deposited metal in galvanic series, and the metal ion in template is reduced first, and is deposited
To substrate material surface；And the metal ion in main salt negative potential and displacement reaction double action under, with restore after mould
Metal in plate agent gradually alternate template agent metal and is deposited on substrate material surface as nucleus；The addition of trace mineral supplement,
Its space steric effect and its package action to metallic particles can be utilized, the form parameter of taper nanoparticle is adjusted, divides
Cloth density and deposition velocity regulate and control the size of catalyst particle.
The preparation method combines chemistry displacement reaction, constant potential electro-deposition techniques, has easy to operate, repeatable
Strong advantage, prepared electrode surface uniformly, be very suitable to improve CO2The rate of electrochemical reducting reaction.
Compared with electrode fabrication derived from the metal oxide of existing heat treating process preparation, using present invention side
Electrode prepared by method, has a characteristic that
1) electrode surface catalyst particle is that nanometer is tapered.The study found that in electrochemical system, tapered catalyst particle
Tip portion electric field strength increased substantially with the reduction of tip diameter, cause tip near sites alkali metal ion it is dense
Degree dramatically increases, and this alkali metal ion can by with CO2Noncovalent interaction improve catalyst surface active position week
The CO enclosed2Concentration, to increase considerably CO2The reaction rate of electrochemical reduction changes the product distribution of ERC reaction；Simultaneously should
The electrode of feature, which has, improves C2H4The advantage of selectivity.
2) preparation method is good to the universality of electrode base materials.Electrode preparation method proposed by the present invention, is not only suitable for
The metal base material of sheet densification, moreover it is possible to obtain good catalyst particle distribution on porous carbon-based material surface.
Detailed description of the invention:
Fig. 1 is the XRD diagram that surface prepared by embodiment 3 is CuNA structure electrode.
Fig. 2 is the surface topography that surface prepared by embodiment 3 is CuNA structure electrode.
Fig. 3 is selectivity of the electrode to ERC reaction product of the tapered catalyst particle of nano surface prepared by embodiment 3,
It is compared simultaneously with comparative example 1.
Specific embodiment
The following are specific embodiments of the present invention, but the present invention is not limited to provided embodiments.
Comparative example 1
1. copper foil pre-processes: being 99.5%, with a thickness of 100 microns, area 7cm with purity2Copper foil as substrate material
Material, first at room temperature, it is successively soaked in acetone and carries out oil removal treatment, and the oil removing time is 30min, with high-purity after taking-up
After argon gas drying；Then it being impregnated in the dilute hydrochloric acid that volume fraction is 38% and is chemically treated again, the processing time is 60min,
Remove the impurity such as oxide on surface.It is finally rinsed with a large amount of deionized waters to neutrality, is dried up with high-purity argon gas；
2. copper foil electrode electrochemical catalysis restores CO2: in improved H-type electrolytic cell, it is separately added into anode and cathode chamber
150ml 0.1M KHCO3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses the NF115 of DuPont production as yin
The diaphragm of anode cavities.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas, CO2Flow control be
60sccm.After 40min, using the copper foil Jing Guo chemical pretreatment as working electrode, Pt piece is to electrode, and saturated calomel electrode is ginseng
Compare electrode.The electrochemical reducting reaction of CO2 is carried out under -0.96V~1.46V (relative to saturated calomel electrode) operating voltage,
Each current potential keeps 30min, and reaction end gas is passed through the quantitative detection that gas-chromatography carries out gaseous product, and product liquid uses ion
Chromatography carries out quantitative analysis.
Product analysis result: in -2.0V, the kinetic current density of ERC is 15mAcm-2,CH4And C2H4Faradic efficiency
The faradic efficiency of respectively 31.5% and 6.8%, HCOOH and CO are respectively 16.2% and 10.7%, H2Faradic efficiency
It is 38.2%.
Comparative example 2
1, charcoal felt pre-processes: being 85%, with a thickness of 2 millimeters, area 7cm with porosity2Charcoal felt as base material,
At room temperature, it is soaked in acetone and carries out oil removal treatment, the oil removing time is 50min, after being dried up after taking-up with high-purity argon gas；
2, the electro-deposition of the tapered Au catalyst particle of nanometer
Firstly, being formulated as follows the NaAuCl that concentration is 30mM using deionized water4·2H2The plating solution of O；
Then, pH is adjusted to 8.5. using the NaOH that concentration is 8M
Plating solution is transferred in 80 DEG C of constant temperature of water-bath by third, to pass through pretreated charcoal felt as working electrode, with platinum
Piece is used as to electrode, and Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 600rpm.Electricity is heavy
Product current potential is 0.8V, sedimentation time 10min.
4th, post-depositional charcoal felt electrode (gas-diffusion electrode) is taken out, is rinsed with a large amount of deionized waters, uses high-purity argon gas
Drying.Obtained charcoal felt electrode surface is yellow, and wherein Au particle is spherical in shape, and Au bulb diameter is 15~50nm.
3. the electrode electro Chemical catalysis reduction CO that surface is spherical shape Au particle2: in improved H-type electrolytic cell, anode and cathode
150ml 0.1M KHCO is separately added into chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution is produced using DuPont
Diaphragm of the NF115 as anode and cathode chamber.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas, CO2
Flow control be 60sccm.After 40min, using the charcoal felt by electrochemical deposition spherical shape Au particle as working electrode, Pt piece is
To electrode, saturated calomel electrode is reference electrode.Under -0.8V~-1.5V (relative to saturated calomel electrode) operating voltage into
Row CO2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through gas-chromatography and carries out determining for gaseous product
Amount detection, product liquid carry out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 40mAcm in the kinetic current density of -1.2V, ERC-2, the farad of HCOOH and CO
Efficiency is respectively 2.4% and 45.30%, H2Faradic efficiency be 53.2%.
Embodiment 1
1. carbon paper pre-processes: being 78%, with a thickness of 190 microns, area 3cm with porosity2TGP-H-060 carbon paper
It is successively soaked in acetone at room temperature and carries out oil removal treatment as base material by (production of Toray company), when oil removing
Between be 45min, after being dried up after taking-up with high-purity argon gas；
2. the electro-deposition of nanometer tapered Cu catalyst particle
Firstly, being formulated as follows the plating solution of composition using deionized water: 0.5mM CuAc2·H2O+0.5mM NiCl2·6H2O
+0.05M KH2PO2+5mM HC6H5O7+0.05MH3BO3+5ppmTriton-100；
Then, pH is adjusted to 8.0. using the KOH that concentration is 8M
Plating solution is transferred in 40 degrees Celsius of constant temperature of water-bath by third, using the pretreated carbon paper of process as working electrode,
Using platinized platinum as to electrode, Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 800rpm.
Electro-deposition current potential is -0.95V, sedimentation time 60min.
4th, post-depositional copper electrode (also known as gas-diffusion electrode) is taken out, is rinsed with a large amount of deionized waters, use is high-purity
Argon gas drying.Obtained copper electrode surface is kermesinus, and wherein copper particle is tapered in nanometer, and cone bottom diameter is 0.05~0.5
μm, a height of 0.5~1.5 μm is bored, the load amount of Cu particle is 2.5mg cm-2。
3. the electrochemical pre-treatment that surface is the gas-diffusion electrode of the tapered copper particle of nanometer: in CO2The 0.1M of saturation
NaHCO3In solution, the 2273 type potentiostats produced using Princeton company, control reduction current is 0.1mA cm-2, also
The former time is 60min.After reduction, electrode surface is kermesinus.
4. the gas-diffusion electrode electrochemical catalysis that surface is the tapered copper particle of nanometer restores CO2: it is electrolysed in improved H-type
Chi Zhong is separately added into 150ml 0.1M KHCO in anode and cathode chamber3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses
Diaphragm of the NF115 of DuPont production as anode and cathode chamber.Before test, purity is passed through into cathode cavity first is
99.995% CO2Gas, CO2Flow control be 60sccm.After 40min, expanded with the gas of surface electro-deposition taper Cu particle
Electrode is dissipated as working electrode, and Pt piece is to electrode, and saturated calomel electrode is reference electrode.- 1.3V~-2.1V (relative to
Saturated calomel electrode) CO is carried out under operating voltage2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through
Gas-chromatography carries out the quantitative detection of gaseous product, and product liquid carries out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 62mAcm in the kinetic current density of -2.0V, ERC-2,CH4、C2H4And C2H6's
Faradic efficiency is respectively 18%, 35% and 0.6%, and the faradic efficiency of HCOOH and CO are respectively 15.3% and 6.4%, H2
Faradic efficiency be 24%.
Embodiment 2
1, indium foil pre-processes: being 99.9%, with a thickness of 200 microns, area 5cm with purity2Indium foil as substrate material
Material, first at room temperature, it is successively soaked in dehydrated alcohol and carries out oil removal treatment, and the oil removing time is 30min, is used after taking-up
After high-purity argon gas drying；Then be impregnated in again volume fraction be 5% dilute hydrochloric acid in be chemically treated, processing the time be
30min, the impurity such as removal oxide on surface.It is finally rinsed with a large amount of deionized waters to neutrality, is dried up with high-purity argon gas；
2, the electro-deposition of the tapered In catalyst particle of nanometer
Firstly, being formulated as follows the plating solution of composition using deionized water: 5mM InCl3+10mM Ni(NO3)2·6H2O+1.0M
NH4H2PO2+50mM NH4C6H5O7·2H2O+5MH3BO3+500ppmPEG(10,000)；
Then, pH is adjusted to 10.0. using ammonium hydroxide
Plating solution is transferred in 60 degrees Celsius of constant temperature of water-bath by third, using the pretreated indium foil of process as working electrode,
Using platinized platinum as to electrode, Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 800rpm.
Electro-deposition current potential is -0.5V, sedimentation time 20min.
4th, post-depositional indium foil electrode is taken out, is rinsed with a large amount of deionized waters, is dried up with high-purity argon gas.It is obtained
Indium foil electrode surface is dark gray, and wherein indium particle is tapered in nanometer, and cone bottom diameter is 0.05~0.1 μm, cone a height of 0.6~2
μm, the load amount of In particle is 3.0mg cm-2。
4. the electrochemical pre-treatment that surface is the electrode of the tapered indium particle of nanometer: in CO2The 0.1M KHCO of saturation3Solution
In, the 2273 type potentiostats produced using Princeton company, control reduction current is 0.3mA cm-2, the recovery time is
20min.After reduction, electrode surface is dark gray.
5. the electrode electro Chemical catalysis reduction CO that surface is the tapered indium particle of nanometer2: in improved H-type electrolytic cell, yin
150ml 0.1M KHCO is separately added into anode cavities3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses DuPont company
Diaphragm of the NF115 of production as anode and cathode chamber.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas
Body, CO2Flow control be 60sccm.It is electric using the indium foil of surface electro-deposition nanometer taper In particle as work after 40min
Pole, Pt piece are to electrode, and saturated calomel electrode is reference electrode.It works in -1.1V~-2.1V (relative to saturated calomel electrode)
CO is carried out under voltage2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 53mAcm in the kinetic current density of -0.8V, ERC-2, the farad of HCOOH and CO
Efficiency is respectively 98% and 0.3%, H2Faradic efficiency be 1.6%.
Embodiment 3
1. copper foil pre-processes: being 99.5%, with a thickness of 100 microns, area 7cm with purity2Copper foil as substrate material
Material, first at room temperature, it is successively soaked in acetone and carries out oil removal treatment, and the oil removing time is 30min, with high-purity after taking-up
After argon gas drying；Then it being impregnated in the dilute hydrochloric acid that volume fraction is 38% and is chemically treated again, the processing time is 60min,
Remove the impurity such as oxide on surface.It is finally rinsed with a large amount of deionized waters to neutrality, is dried up with high-purity argon gas；
2. the electro-deposition of nanometer tapered Cu catalyst particle
Firstly, being formulated as follows the plating solution of composition using deionized water: 0.05M CuSO4·5H2O+0.005M NiSO4·
6H2O+0.6M NaH2PO2+0.1M NaC6H5O7·2H2O+0.3MH3BO3+200ppmPEG(6,000)；
Then, pH is adjusted to 9.5. using the NaOH that concentration is 8M
Plating solution is transferred in 55 degrees Celsius of constant temperature of water-bath by third, using the pretreated copper foil of process as working electrode,
Using platinized platinum as to electrode, Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 400rpm.
Electro-deposition current potential is -0.95V, sedimentation time 30min.
4th, post-depositional copper electrode is taken out, is rinsed with a large amount of deionized waters, is dried up with high-purity argon gas.Obtained copper
Electrode surface is crineous, from figure 2 it can be seen that wherein copper particle is tapered in nanometer, cone bottom diameter is 0.5~1 μm, cone
A height of 1~3 μm, the load amount of Cu particle is 1.0mg cm-2。
3. the electrochemical pre-treatment that surface is the electrode of the tapered copper particle of nanometer: in CO2The 0.1M KHCO of saturation3Solution
In, the 2273 type potentiostats produced using Princeton company, control reduction current is 0.3mA cm-2, the recovery time is
30min.After reduction, electrode surface is kermesinus.
4. the electrode electro Chemical catalysis reduction CO that surface is the tapered copper particle of nanometer2: in improved H-type electrolytic cell, yin
150ml 0.1M KHCO is separately added into anode cavities3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses DuPont company
Diaphragm of the NF115 of production as anode and cathode chamber.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas
Body, CO2Flow control be 60sccm.After 40min, using the copper foil Jing Guo chemical pretreatment as working electrode, Pt piece is to electricity
Pole, saturated calomel electrode are reference electrode.It is carried out under -0.96V~1.46V (relative to saturated calomel electrode) operating voltage
CO2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through gas-chromatography and carries out quantifying for gaseous product
Detection, product liquid carry out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 62mAcm in the kinetic current density of -2.0V, ERC-2,CH4And C2H4Faraday
Efficiency is respectively 15% and 23%, and the faradic efficiency of HCOOH and CO are respectively 29% and 8%, H2Faradic efficiency be
25%.
Embodiment 4
1, charcoal cloth pre-processes: being 60%, with a thickness of 500 microns, area 10cm with porosity2Charcoal cloth as substrate material
Material, at room temperature, it is successively soaked in dehydrated alcohol and carries out oil removal treatment, and the oil removing time is 30min, with high-purity after taking-up
After argon gas drying；
2, the electro-deposition of the tapered Ag catalyst particle of nanometer
Firstly, being formulated as follows the plating solution of composition using deionized water: 10mM AgNO3+2mM NiCl2·6H2O+0.1M
KH2PO2+10mMKC6H5O7·2H2O+1MH3BO3+ 100ppm oleyl alcohol；
Then, pH is adjusted to 9 using the KOH that concentration is 8M.
Plating solution is transferred in 70 DEG C of constant temperature of water-bath by third, using the process pretreated charcoal cloth of oil removing as working electrode,
Using platinized platinum as to electrode, Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 200rpm.
Electro-deposition current potential is -0.3V, sedimentation time 5min.
4th, post-depositional charcoal cloth electrode (gas-diffusion electrode) is taken out, is rinsed with a large amount of deionized waters, uses high-purity argon gas
Drying.Obtained charcoal cloth electrode surface is dark gray, and wherein Ag particle is tapered in nanometer, and cone bottom diameter is 0.05 μm~1.5
μm, a height of 1~2 μm is bored, the load amount of Ag particle is 0.5mg cm-2。
6. the electrochemical pre-treatment that surface is the gas-diffusion electrode of the tapered Ag particle of nanometer: in CO2The 0.1M of saturation
NaHCO3In solution, the 2273 type potentiostats produced using Princeton company, control reduction current is 0.2mA cm-2, also
The former time is 30min.After reduction, electrode surface is dark gray.
7. the electrode electro Chemical catalysis reduction CO that surface is the tapered Ag particle of nanometer2: in improved H-type electrolytic cell, yin
150ml 0.1M KHCO is separately added into anode cavities3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses DuPont company
Diaphragm of the NF115 of production as anode and cathode chamber.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas
Body, CO2Flow control be 60sccm.It is electric using the charcoal cloth of surface electro-deposition nanometer taper Ag particle as work after 40min
Pole, Pt piece are to electrode, and saturated calomel electrode is reference electrode.It works in -0.7V~-1.5V (relative to saturated calomel electrode)
CO is carried out under voltage2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 37mAcm in the kinetic current density of -1.3V, ERC-2, the farad of HCOOH and CO
Efficiency is respectively that the faradic efficiency of 3% and 91%, H2 is 7.6%.
Embodiment 5
1, charcoal felt pre-processes: being 95%, with a thickness of 1.5 millimeters, area 7cm with porosity2Charcoal felt as substrate material
Material, at room temperature, is soaked in acetone and carries out oil removal treatment, and the oil removing time is 50min, is dried up after taking-up with high-purity argon gas
Afterwards；
2, the electro-deposition of the tapered Au catalyst particle of nanometer
Firstly, being formulated as follows the plating solution of composition using deionized water: 30mM NaAuCl4·2H2O+4mM NiSO4·6H2O
+0.3M NaH2PO2+30mM NaC6H5O7·2H2O+2MH3BO3+50ppmPEG(2,000)；
Then, pH is adjusted to 8.5. using the NaOH that concentration is 8M
Plating solution is transferred in 80 DEG C of constant temperature of water-bath by third, to pass through pretreated charcoal felt as working electrode, with platinum
Piece is used as to electrode, and Ag/AgCl (KCl saturated solution) makees reference electrode, electro-deposition is carried out under the mixing speed of 600rpm.Electricity is heavy
Product current potential is 0.8V, sedimentation time 10min.
4th, post-depositional charcoal felt electrode (gas-diffusion electrode) is taken out, is rinsed with a large amount of deionized waters, uses high-purity argon gas
Drying.Obtained charcoal felt electrode surface is dark yellow, and wherein Au particle is tapered in nanometer, and cone bottom diameter is 0.1~2 μm, cone
A height of 0.8~3 μm, the load amount of A particle is 1.8mg cm-2。
8. the electrochemical pre-treatment that surface is the electrode of the tapered Au particle of nanometer: in CO2The 0.1M KHCO of saturation3Solution
In, the 2273 type potentiostats produced using Princeton company, control reduction current is 0.5mA cm-2, the recovery time is
20min.After reduction, electrode surface is dark yellow.
9. the electrode electro Chemical catalysis reduction CO that surface is the tapered Au particle of nanometer2: in improved H-type electrolytic cell, yin
150ml 0.1M KHCO is separately added into anode cavities3Aqueous solution and 50ml 0.1M KHCO3Aqueous solution uses DuPont company
Diaphragm of the NF115 of production as anode and cathode chamber.Before test, the CO that purity is 99.995% is passed through into cathode cavity first2Gas
Body, CO2Flow control be 60sccm.It is electric using the charcoal felt of surface electro-deposition nanometer taper Au particle as work after 40min
Pole, Pt piece are to electrode, and saturated calomel electrode is reference electrode.It works in -0.8V~-1.5V (relative to saturated calomel electrode)
CO is carried out under voltage2Electrochemical reducting reaction, each current potential keeps 30min, and reaction end gas is passed through gas-chromatography and carries out gas
The quantitative detection of product, product liquid carry out quantitative analysis using ion chromatography.
Product analysis result are as follows: be up to 40mAcm in the kinetic current density of -1.2V, ERC-2, the farad of HCOOH and CO
Efficiency is respectively 1% and 94.5%, H2Faradic efficiency be 4.4%.
Claims (10)
1. a kind of CO2Electrochemical reduction electrode, it is characterised in that: electrode is deposited with metal catalytic particles by substrate and thereon
Decorative layer composition, the metal catalytic particles in nanometer it is tapered；Wherein nanometer cone height is 1~10 μm, and cone bottom diameter is
0.2~2 μm；It is preferred that bore it is 2~7 μm high, preferably cone bottom diameter be 0.3~1.2 μm；
The tapered catalyst particle of the nanometer is 0.1~3.0mgcm in the loading in substrate-2, preferably loading be 0.5~
1.8mgcm-2。
2. a kind of electrode preparation method described in claim 1, it is characterised in that: in the alkalescent comprising template and additive
It deposits in liquid, is heating under stirring condition, obtained using chemistry displacement reaction with the technology that electrochemistry potentiostatic electrodeposition combines
?；Wherein, deposition liquid component includes soluble salt solutions (main salt), template, complexing agent, the stabilizer, reduction of deposited metal
Agent and additive, main salt: template: the molar ratio control range of additive is 104:103: 1~103:102: 1, preferably compare
Example range is 0.6 × 104:0.4×103: 1~0.15 × 104: 0.2 × 103:1；The pH range for depositing liquid is 8~10；
The chemistry displacement reaction occurs between the metal of metallic and main salt that template deposits.
3. electrode preparation method as claimed in claim 2, which comprises the steps of:
1) processing of impurity is removed to substrate；It is dried up after being rinsed with water after processing to neutrality with inert atmosphere；
2) base material is immersed in deposition liquid, adjusts bath temperature and mixing speed, carry out chemical displacement and constant potential
It deposits, is dried up after being rinsed with water after deposition to neutrality with inert atmosphere；Surface is obtained with the tapered catalyst particle of compact nanometer
Electrode；
3) there is the electrode of the tapered catalyst particle of compact nanometer to carry out electrochemical reduction pretreatment surface, obtains CO2Electrochemistry
Electrode is used in reduction.
4. electrode preparation method described in accordance with the claim 3, it is characterised in that:
The base material is metal or charcoal based porous materials, the metal be one of Cu, In, Ag, Au or two kinds with
On, metal quality content is not less than 99.5%；Charcoal based porous materials are one of carbon paper, carbon felt or carbon cloth, porosity 60-
95%；Shapes of substrates is flake, thickness 0.05mm-2mm；
The base material decontamination processing, including oil removing and chemical treatment；Wherein, oil removal process is molten in polarity at room temperature
At least 30min is impregnated in agent；To impregnate in the hydrochloric acid solution that mass concentration is 1%~38%, soaking time is for chemical treatment
5min~60min is dried up after cleaning up after processing with inert atmosphere；
The polar solvent is one of dehydrated alcohol, acetone, and inert atmosphere is one of nitrogen, argon gas or two kinds.
5. according to preparation method described in claim 2 and 3, it is characterised in that: the soluble salt solutions of the deposited metal
For one of halide, sulfate, nitrate, acetate；The metal be one of Cu, In, Ag, Au or two kinds with
On；The concentration for depositing metal ions in liquid is 0.5mM~50mM, and preferred ion concentration is 5mM~30mM；
The template is one of nickel nitrate, nickel chloride, nickel sulfate；
The reducing agent is soluble hypophosphite, including in sodium hypophosphite, ammonium hypophosphite, ortho phosphorous acid potassium
It is a kind of, wherein Hypophosphite concentration is 0.05M~1.0M in deposition liquid, and preferred concentration range is 0.1M~0.5M；
The stabilizer is boric acid, and concentration is 0.05M~5M in deposition liquid, and preferred concentration is 0.1M~2M；
The complexing agent is one of citric acid or citrate, including ammonium citrate, sodium citrate, potassium citrate；It is heavy
The concentration of citrate is 5mM~100mM in hydrops, and preferred concentration is 10mM~50mM；
The additive is polyethylene glycol type surfactant, including molecular weight is lower than 20,000 polyethylene glycol (PEG), oil
Alcohol, Qula lead to one of Triton-100.
6. according to preparation method described in claim 2 or 3, it is characterised in that: the plating solution pH value adjustment uses concentrated ammonia liquor
Or the hydroxide of alkali metal；
The electrodeposition temperature is 40 DEG C~80 DEG C, and mixing speed is 200rpm~800rpm.
7. according to preparation method described in claim 2 or 3, it is characterised in that: the electro-deposition current potential sinks than corresponding
Product metal the low about 0.3~1.0V of equilibrium potential, sedimentation time be 5min~90min, the preferred deposition time be 10min~
60min。
8. preparation method described in accordance with the claim 3, it is characterised in that: the electrochemical reduction is pre-processed in CO2Saturation
It is carried out in salting liquid, the salting liquid is the sodium bicarbonate or saleratus that concentration is 0.1~0.5M.
9. according to preparation method described in claim 3 or 8, it is characterised in that: the electrochemical reduction pretreatment, processing electricity
Stream is 0.1~0.5mAcm-2, pretreatment time is 20min~60min.
10. a kind of application of electrode described in claim 1, it is characterised in that: the application of electrode is in carbon dioxide electrochemistry
In reduction.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113061931A (en) * | 2019-12-13 | 2021-07-02 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Preparation method of electrode catalyst for electrochemical reduction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120040462A (en) * | 2010-10-19 | 2012-04-27 | 한양대학교 산학협력단 | Method for fabricating nanostructure and method for fabricating electronic devices using the same |
| CN103789807A (en) * | 2014-01-06 | 2014-05-14 | 中国科学院合肥物质科学研究院 | Nano tube array consisting of noble metal nano structure units, preparation method for nano tube array and application of nano tube array in organic molecule detection |
| CN105304910A (en) * | 2014-07-01 | 2016-02-03 | 中国科学院大连化学物理研究所 | Electrode of hydrocarbon produced by carbon dioxide through electrochemical reduction and preparation and application of electrode |
| CN106567041A (en) * | 2016-11-09 | 2017-04-19 | 东南大学 | Preparation method suitable for silica gel key gold plated nickel material |
| CN106868536A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The Carbon dioxide electrochemical reduction preparation of porous copper electrode and its electrode and application |
-
2017
- 2017-11-30 CN CN201711237054.XA patent/CN109852991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120040462A (en) * | 2010-10-19 | 2012-04-27 | 한양대학교 산학협력단 | Method for fabricating nanostructure and method for fabricating electronic devices using the same |
| CN103789807A (en) * | 2014-01-06 | 2014-05-14 | 中国科学院合肥物质科学研究院 | Nano tube array consisting of noble metal nano structure units, preparation method for nano tube array and application of nano tube array in organic molecule detection |
| CN105304910A (en) * | 2014-07-01 | 2016-02-03 | 中国科学院大连化学物理研究所 | Electrode of hydrocarbon produced by carbon dioxide through electrochemical reduction and preparation and application of electrode |
| CN106868536A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The Carbon dioxide electrochemical reduction preparation of porous copper electrode and its electrode and application |
| CN106567041A (en) * | 2016-11-09 | 2017-04-19 | 东南大学 | Preparation method suitable for silica gel key gold plated nickel material |
Non-Patent Citations (1)
| Title |
|---|
| HONG LI等: "In Situ Growth of Densely Packed Single-Crystal Copper Nanocone Structure Films with Condensate Microdrop Self-Removal Function on Copper Surfaces", 《ADV. MATER. INTERFACES》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061931A (en) * | 2019-12-13 | 2021-07-02 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Preparation method of electrode catalyst for electrochemical reduction |
| CN113061931B (en) * | 2019-12-13 | 2022-06-03 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Preparation method of electrode catalyst for electrochemical reduction |
| CN112647099A (en) * | 2020-11-02 | 2021-04-13 | 江苏大学 | Preparation of transition metal nano catalyst by electrodeposition method and application thereof in electrocatalysis of CO2Reduction of |
| CN112481663A (en) * | 2020-12-15 | 2021-03-12 | 中南大学深圳研究院 | Preparation method of copper nanoflower applied to efficient carbon dioxide reduction reaction to generate ethylene |
| CN112853392A (en) * | 2021-01-11 | 2021-05-28 | 清华大学深圳国际研究生院 | Alkaline electrolyzed water anode and preparation method thereof |
| CN112853392B (en) * | 2021-01-11 | 2022-03-18 | 清华大学深圳国际研究生院 | Alkaline electrolyzed water anode and preparation method thereof |
| CN112941553A (en) * | 2021-01-27 | 2021-06-11 | 天津理工大学 | Preparation method and application of three-dimensional nano tip copper electrode |
| CN113373462A (en) * | 2021-05-21 | 2021-09-10 | 南京理工大学 | For electrochemical reduction of CO2Membrane type liquid flow electrolytic cell and testing process |
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